We report an amidinato ligand-supported series of magnesium complexes obtained from the insertion of a magnesium-carbon bond into a carbon-nitrogen double bond of different carbodiimides and α-diimine ligands. The magnesium complexes [Mg(CH2Ph){CyNC(CH2Ph)NCy}]2 (1), [Mg(CH2Ph){iPrNC(CH2Ph)NiPr}]2 (2) and the homoleptic [Mg{tBuNC(CH2Ph)NtBu}2] (3) (Cy = cyclohexyl, iPr = isopropyl, tBu = tert-butyl) were prepared by the reaction of dibenzyl magnesium [Mg(CH2Ph)2(Et2O)2] with the respective carbodiimides either in 1:1 or 1:2 molar ratio in toluene. The analogous reaction of [Mg(CH2Ph)2(Et2O)2] with the N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (Dipp2DAD) ligand afforded the corresponding homoleptic magnesium complex [Mg{DippNC(CH2Ph)CH2NDipp}2] (4) (Dipp = 2,6 diisopropylphenyl) in good yield. The solid-state structures of magnesium complexes 1-4 were confirmed by single-crystal X-ray diffraction analysis. It was observed that in each case, a magnesium-carbon bond was inserted into the carbon-nitrogen double bond of either carbodiimides or Dipp2DAD resulting in a monoanionic amido-imino ligand. In a further reaction between 1 and N-aryliminopyrrolyl ligand 2-(2,6-iPr2C6H3NCH)C4H3NH (ImpDipp-H) in 1:2 molar ratio, a new magnesium complex [Mg(ImpDipp)2{CyNC(CH2Ph)NHCy}] (5), with one amidinato and two aryliminopyrrolyl ligands in the coordination sphere, was obtained in good yield. In contrast, the homoleptic magnesium complex 4 reacted with one equivalent of N-aryliminopyrrolyl ligand (ImpDipp-H) to produce another mixed ligated magnesium complex [Mg{DippNC(CH2Ph)CH2NDipp}(ImpDipp)] (6), with a benzylated DAD ligand and aryliminopyrrolyl ligands in the coordination sphere. Further reaction of complex 4 with benzyl alcohol (PhCH2OH) afforded the third mixed ligated magnesium complex [Mg{DippNC(CH2Ph)CH2NDipp}(OCH2Ph)2] (7) in very good yield. The magnesium complexes 5-7 were characterised using standard analytical/spectroscopic techniques and their solid-state structures were established by single-crystal X-ray diffraction analysis. This journal is © The Royal Society of Chemistry 2015.